Conversion of hydrocarbons



Fatenled Sept. 25, 1945 CONVERSION OF HYDRDCARBONS William J. Mattox, Riverside, Ill., aseignor to Universal Oil Products Company, Chicago, 111.; a corporation of Delaware j No Drawing.

.8 Claims.

This application is a continuation-in-part of my co-pending application Serial No. 430,502, filed February 11, 1942, now U. S. Patent 2,360,- dii, issued October 17, 1944.

This invention relates to the treatment of a mlxture qii polyalkylated cyclic hydrocarbons and non-alkylated cyclic hydrocarbons whereby alkyl substituent groups are transferred, and more particularly to the transfer of an alkyl group or groups from a polyalkylated aromatic hydrocarhon to a non-alkylated aromatic hydrocarbon in order to produce the mono-alkylated aromatic hydrocarbon.

Various processes have been used for producing mono-alkylated aromatic hydrocarbons as, for example, by the alkyiation of benzene with an olefin or by the cyclization of aliphatic hydrocarbons containing at least seven carbon atoms. muting the course of the alkylation and cyclication reactions, there is also produced varying amounts of allcylated aromatic hydrocarbons containing two or more substituent groups. For example, in the alkylation of benzene with ethylene to produce 'mono-ethylbenzene, there is also produced varying amounts of diethylbenzene. The present invention relates to a method for converting the polyalkylated aromatics into the a mixture of dimethylbenzene and benzene to contact with alumina and hydrogen chloride at a temperature of from about 350 to about 700 C. Suitable catalysts comprise alumina Produced by the controlled calcination of a hydrated alu- 4 minum oxide either naturally occurring or synthetic. The preferred catalyst comprises gamma alumina as the only form of aluminum oxide present. This may be produced by the controlled calcination of natural or synthetic hydrated aluminum oxides at temperatures above about 500 C. and preferably not in excess of 900 C. for a sumcient length of time to convert the hydrated oxide into the gamma form without leaving sub- Application September 30, 1944, Serial No. 656,853

out converting any of the gamma alumina into the alpha form. If the latter condition occurs the catalyst will be substantially inert or at least of greatly reduced activity.

Naturally occurring minerals or earths containing alumina may also be used in the process although they are not necessarily equivalent to one another or to the synthetic forms of alumina. Bauxite which may be calcined to convert it into gamma alumina is a particularly good example of naturally occurring earth. Other aluminiferous clays may be used.

Naturally occurring aluminiferous earths may be used in the process after being treated chemically, for example, with mineral acids, such as hydrochloric acid, followed by washing to remov'e soluble salts. These materials are further improved by calcination prior to use in the process.

Another type of clay which may be of considerable benefit comprises a synthetic mixture of silica and alumina prepared by the separate or simultaneous precipitation oi hydrogels of the components from soluble compounds. These composites may be washed, dried, and calcined prior to use in the process.

The preferred hydrogen halide is hydrogen chloride although other hydrogen halides such as hydrogen bromide, hydrogen iodide and hydrogen fluoride may also be used. These are not necessarily exactly equivalent for my process.

In accordance with the invention a polyalkylated aromatic and a non-alkylated aromatic are contacted with the alumina-containing cats lyst at a temperature of from about 350 to about 700 C., and preferably from about 400 to about 600 C. Under these conditions a transfer of the alkyl group from the polyalkyiated aromatic to the non-alkylated aromatic occurs to produce the mono-alkylated aromatic hydrocarbon. Thus, xylene and benzene may be converted into toluene. Similarly, diethylbenzene and benzene may be converted into mono-ethylbenzene.

Atmospheric, superatmospheric or subatmospheric pressures may be employed. Good results may be obtainedat pressures of from atmospheric to about 100 pounds per square inch. The pressure to be employed in any given operation will depend upon the temperature and space ve' locity as will be hereinafter set forth.

The space velocity employed may vary up to about 20, depending on the catalyst and the temperature. Higher space velocities may be used with more active catalysts and for a given stantial amounts of the hydrated oxide and with-- 6 catalyst at higher temperatures. Normally an 4 tained in tubes or chambers.

I ass.

hourly. liquid space velocity of about 0.2 to 5 is used when employing temperatures Within the rsnsevot about JO-800 C. The space vclociw as used herein is defined as the volumes of liquid charge. per volume of, catalyst per hour. the liq-'- uid being measured at room temperature.

To successfully carry out my invention it is necessary to correlate the conditions 01 tempersture, pressure, and space velocity and this in turn depends to a certain extent upon the cste= lyst employed. Certain forms of the sis. or alumina-containing catalysts are more active than others and higher space velocities at a. given temperature may be .used. Higher pressures should not he used with the hiehertemperetures in order to avoid undesirable cracking reactions. 1 Lower specs velocities permit the use of the lower temper-dimes. I

The quantity of hydrogen holide employed may vary over a. considerable range hut'normully otleast 1 incl per cent is rmuired. There is little benefit to h realized in using more than soul molar proportions oi-hydrocsrhon and chosen holidc. I do not, however, limit myself to this upper limit since it is possible to use higher ratios, even though in most cases there is no perticulor advantage in doing so.

The hydrogen hslide may he sepuruted and recycled to the process. It usually is not necessary to free the hydrogen helide completely oi light hydrocarbon asses.

The unconverted polyolhyloted nrometic hydrocarbon may be :5 fr the desired mono-alkylated hydrocarbon hy fractionation orother suitable means, and the unconverted pounds may. be recycled for further conversion.

The catalyst may he used in the to of grain-=- ules or preformed particles or in the form oi pow= ders. The hydrocarbons undergoing treetment may he passed through beds or the alumina. or

alumina-containing cstolyst, which may be con-=- Th reaction zone may or may not be externally hosted. The cet= slyst may also be suspended in the hydrocarbon vapors in the form of epowder end passed through a nested reaction zone. In soother modincstion the hydrocarbons and hydrogen hslide may he contacted with fluidized powdered nluminn. My invention is not limited to any perticuler sppe retus or method of carrying out the contsct ins.

Under certain conditions and when using cer= tain catalysts it may be desirable to odd s rel stively inert gas such as steam. This is of some utility, for exple, when employing-the synthetic silics-elumine, type oi cstnlyst. When de sired. hydrogen or o hydrogen-containing on; may be supplied to the reaction zone. I

Since benzene is more stable at high temperat tures than the polyalkyleted herizenes, one method oi operation may comprise hosting the benzene in sseparste heating coil to e. temperature in en= cess of the reaction .tempereture end then mix in: the heated products with the polyolmlnted benzenes which hed heen'eepsretely heated to e lower temperature. The heating of the seperste streams must be controlled so that, upon o= ture, the desired resctiou psi-store is obtoincd. When desired. odditlonol heet rosy he supplied to the reaction zone by moons of heated rech'culnted In general, it may he ststed'thnt the ease of transfer of alkyl groups increases with increes= inxmoleculsr weight of the dim]. groups up to e. certain point, after which increasing cunts messes of decomposition reactions occur. Thus,

groups, such as in mlenes and mesitylene, oregroups are transferred still more easily. When substituent. groups having five or more carbon atoms are treated in accordance with the intcn= tion, there is an increasing tendency for side reactions to occur and it is necessary to use the more moderate conditions oi operation.

The operating conditions will also he varied with the types of. aromatics which are tre ed in the present invention. The present process be employed effectively to transfer allryl groups from either mono-nuclear or polynucleor cromstic hydrocarbons. Thus, methyl, ethyl, propyl and butyl substituent groups may be transferred frompolyalwlated benzenes or polyolwloted naphthalenes to either benzene or naphthalene.

Another factor which requires considerntlcn in the present process is the ratio of polyellrylsted aromatic to non-alkyleted aromatic. There should be at least one-moi of non-alkyloted nro= rustic hydrocarbon for each substituent group in excess oi one in the polyalkylatod aromatic and preferably an excess of the non-alkylated hydro carbon is used. The ratio of non-sllrylnted oro= rustic hydrocarbon to polyslkylated aromatic may Example A mixture oi hormone and dietlco lhensene redo oi so mole oi benzene to 1 mol oi diothyh hensene y he contacted with on ole. cotolyst in the presence or 1 mol per cent oi hydrossen chloride at ncspheric pressure cteinpei'eturo or 550 C. to produce 86% oi ethylbenzc on c. cnce throush hauls.

I cloim as my invention:

l. A process for the transfer oi ellryi suhstituient groups from a, polyelkyleted sromntic hydro carbon to s non-=ulhylsted srornntic hydrocarbon, which comprises subjecting e proponioned of sold pclyellryleted end said non ellwlnted ero= motic hydrocarbons to contest with an aluminacontsining cetslyst wd o hydrogen helide under ollryl transfer conditions of temperature, pres= sure end e.

2. A process for the transfer oi sllryl. suhstituent groups from n polynlhyloted hormone to benzene,

which comp subjecting a portionerl mixture or sold polyollzyleted benzene and sold hemene contact with en alumina-containing cctslyst .e hydrogen heiide under ellryl trensfer ccndi= tions of temperature, pressure and time.

8. A process :icr the transfer of sllryl suhstitrn out groups from pclysllzylsted oromstic hydro cerlcon to o non-sllryloted aromatic hydrocarbon,

' which comprises subjecting e. proportioned mix ture of said polyollwletcd and sold non-elhyleted aromatic hydrocarbons to contact with on alu- 1o; cents cetelyst one 5t hydrogen hello-o at a temperature or from about 350 to about 4. A process for the transfer of alkyl substituent groups from a polyalkylated benzene to benzene, which comprises subiectinza proportioned mixture 01' said polyalinvlated benzene and said benzene to contact with alumina and hydrogen chloride at a temperature of about 400 to about 800 C.

5. A process for the manufacture of toluene which comprises subjecting a proportioned mixture of apolymethylbenzene and benzene to contact with alumina and hydrogen chloride 'at a. temperature of about 400 to about 600 C.

6. A process for the manufacture of ethylbennone which comprises subjecting a proportioned mixture oi a polyethylbenzene and benzene to contact with alumina and hydroaen chloride at a temperature or about 400 to about 600 C.

7. A process for the manufacture of ieopropylbenzene which comprises subjecting a. proportioned mixture or a polyisopropylbenune and benzene to contact with alumina and hydrozen chloride at a temperature of about 400 to about 600 C. a

8. A process for the manufacture or a monoaikylated aromatic hvdrocarbon by transfer 01' analkyl group from a polyalkyiated aromatic hydrocarbon to a non-alkylated aromatic hydrocar bon. which comprieesheating said non-alkylated aromatic l'is'drooarbonv to a temperature above that required for said alkyl transfer, separately heating aeid polyalkylated aromatic hydrocarbon to a lower temperature, ling the separately heated streams amicon ting the same with a catalyst eompriaina alumina and a hydro. gen halide at aikyi transfer condition: oi temperture, pressure and time. 

